Sustainable Photooxidation using a Subpart-per-million Heavy-Metal-Free Red-Light Photocatalyst DOI
Maxime Lancel,

Tamara Golisano,

Cyrille Monnereau

et al.

ACS Sustainable Chemistry & Engineering, Journal Year: 2023, Volume and Issue: 11(43), P. 15674 - 15684

Published: Oct. 15, 2023

Photochemical activation using red or near-infrared light has recently emerged as a potential remedy for solving fundamental issues in photochemistry such selectivity and scale up. However, this is particularly challenging the case of photooxidation chemistry due to low resistance photobleaching poor solubility photocatalysts absorbing region electromagnetic spectrum. In study, we report use commercially available Si-phthalocyanines robust environmentally friendly class soluble photosensitizers activated under light. Interestingly, while exhibit lower singlet oxygen generation (ϕΔ) quantum yields compared classical photosensitizers, their high stability enables us achieve comparable efficiencies at ultralow catalytic loadings (ppb range). This unique feature provides performances range photooxidative processes substrate concentrations ultimately leading safe efficient solvent-free continuous flow applied multigram-scale synthesis.

Language: Английский

Photocatalyzed Oxygenation Reactions with Organic Dyes: State of the Art and Future Perspectives DOI Open Access
Mattia Forchetta, Francesca Valentini, Valeria Conte

et al.

Catalysts, Journal Year: 2023, Volume and Issue: 13(2), P. 220 - 220

Published: Jan. 18, 2023

Oxygen atom incorporation into organic molecules is one of the most powerful strategies to increase their pharmacological activity and obtain valuable intermediates in synthesis. Traditional oxidizing agents perform very well, but environmental impact low selectivity constitute significant limitations. On contrary, visible-light-promoted oxygenations represent a sustainable method for compounds, since only molecular oxygen photocatalyst are required. Therefore, photocatalytic oxygenation reactions exhibit high atom-economy eco-compatibility. This mini-review collects analyzes recent literature on organo-photocatalysis applications promote selective substrates. In particular, acridinium salts, Eosin Y, Rose Bengal, cyano-arenes, flavinium quinone-based dyes widely used as photocatalysts several transformations alkanes, alkenes, alkynes, aromatic amines, phosphines, silanes, thioethers. this context, organo-photocatalysts proved be highly efficient catalytic terms, showing similar or even superior performances with respect metal-based counterparts, while maintaining impact. addition, given mild reaction conditions, photo-oxygenation processes often display remarkable selectivity, which striking feature late-stage functionalization complex molecules.

Language: Английский

Citations

23
Continuous flow synthesis enabling reaction discovery DOI Creative Commons
Antonella Ilenia Alfano, Jorge García‐Lacuna, Oliver Griffiths

et al.

Chemical Science, Journal Year: 2024, Volume and Issue: 15(13), P. 4618 - 4630

Published: Jan. 1, 2024

This article defines the role that continuous flow chemistry can have in new reaction discovery, thereby creating molecular assembly opportunities beyond our current capabilities. Most notably focus is based upon photochemical, electrochemical and temperature sensitive processes where methods machine assisted processing significant impact on chemical reactivity patterns. These platforms are ideally placed to exploit future innovation data acquisition, feed-back control through artificial intelligence (AI) learning (ML) techniques.

Language: Английский

Citations

16
Continuous Flow Approach for Benzylic Photo-oxidations Using Compressed Air DOI Creative Commons

Ruairí Bannon,

Gary Morrison,

Megan Smyth

et al.

Organic Process Research & Development, Journal Year: 2024, Volume and Issue: 28(8), P. 3307 - 3312

Published: July 24, 2024

A continuous flow approach for the aerobic photo-oxidation of benzylic substrates to ketone and aldehyde products is presented. The resulting process exploits UV-A LEDs (375 nm) in combination with a Corning AFR reactor that ensures effective gas-liquid mixing leads short residence times 1 min. variety are converted their corresponding carbonyl products, scalability demonstrated produce multigram quantities within few hours. Overall, this offers several improvements over alternative oxidation methods due combined use air as an oxidant SAS (sodium anthraquinone-2 sulfonate) water-soluble photocatalyst. greener safer conditions together intensification principles renders attractive further industrial applications.

Language: Английский

Citations

14
Bismuth vanadate: A versatile heterogeneous catalyst for photocatalytic functionalization of C(sp2)–H bonds DOI

Fan‐Lin Zeng,

Hu-Lin Zhu,

Ru-Nan Wang

et al.

CHINESE JOURNAL OF CATALYSIS (CHINESE VERSION), Journal Year: 2023, Volume and Issue: 46, P. 157 - 166

Published: Feb. 23, 2023

Language: Английский

Citations

21
Synthetic Chemistry in Flow: From Photolysis & Homogeneous Photocatalysis to Heterogeneous Photocatalysis DOI

Sitong Feng,

Ren Su

ChemSusChem, Journal Year: 2024, Volume and Issue: 17(16)

Published: April 12, 2024

Abstract Photocatalytic synthesis of value‐added chemicals has gained increasing attention in recent years owing to its versatility driving many important reactions under ambient conditions. Selective hydrogenation, oxidation, coupling, and halogenation with a high conversion the reactants have been realized using designed photocatalysts batch reactors small volumes at laboratory scale; however, scaling‐up remains critical challenge due inefficient utilization incident light active sites photocatalysts, resulting poor catalytic performance that hinders practical applications. Flow systems are considered one solutions for applications light‐driven experienced great success photolytic homogeneous photocatalysis, yet their heterogeneous photocatalysis still development. In this perspective, we summarized progress photocatalytic synthetic chemistry performed flow from view reactor design special focus on photocatalysis. The advantages limitations different systems, as well some considerations strategies discussed.

Language: Английский

Citations

7
Benzoates as photosensitization catalysts and auxiliaries in efficient, practical, light-powered direct C(sp3)–H fluorinations DOI Creative Commons
Shahboz Yakubov, Willibald J. Stockerl, Xianhai Tian

et al.

Chemical Science, Journal Year: 2022, Volume and Issue: 13(47), P. 14041 - 14051

Published: Jan. 1, 2022

Of the methods for direct fluorination of unactivated C(sp3)-H bonds, photosensitization SelectFluor is a promising approach. Although many substrates can be activated with photosensitizing catalysts, issues remain that hamper complex molecules. Alcohol- or amine-containing functional groups are not tolerated, regioselectivity follows factors endogenous to substrate and cannot influenced by catalyst, reactions highly air-sensitive. We report benzoyl serve as efficient photosensitizers which, in combination SelectFluor, enable visible light-powered bonds. Compared previous photosensitizer architectures, benzoyls have versatility function both (i) catalyst simple fluorinations (ii) auxiliaries molecule easily installed removed without compromising yield. Our auxiliary approach substantially decreases reaction's induction period, enables fail under catalytic conditions, (iii) increases kinetic reproducibility, (iv) promotes higher yields, shorter times, on multigram scales, even air. Observations mechanistic studies suggest an intimate 'assembly' prior/after photoexcitation. The allows other EnT photochemistry Examples show how placement proximally directs regioselectivity, where substrate-directed.

Language: Английский

Citations

22
Electrosynthesis ofN,N-dimethylformamide from market-surplus trimethylamine coupled with hydrogen production DOI
Meng Jin,

An-Zhen Li,

Ye Wang

et al.

Green Chemistry, Journal Year: 2023, Volume and Issue: 25(15), P. 5936 - 5944

Published: Jan. 1, 2023

We report an electrochemical oxidation strategy to synthesize DMF directly from market-surplus trimethylamine and couple it with hydrogen production. The reaction was achieved in aqueous medium without any mediator using water as the oxidant.

Language: Английский

Citations

12
Self-Sensitized Photooxidation of Naphthols to Naphthoquinones and the Use of Naphthoquinones as Visible Light Photocatalysts in Batch and Continuous Flow Reactors DOI
Maxime Lancel,

Pierre Zimberlin,

Catherine Gomez

et al.

The Journal of Organic Chemistry, Journal Year: 2023, Volume and Issue: 88(10), P. 6498 - 6508

Published: March 29, 2023

Visible light photooxidation of naphthols to produce naphthoquinones, such as the natural product juglone, has been known for decades and widely utilized benchmark performances a variety photocatalytic systems. We discovered that these transformations can occur without help photocatalyst and, even more intriguingly, photocatatyst-free process provides higher yields compared control experiments utilizing state-of-the-art photocatalysts. In addition, we demonstrate naphthoquinones their corresponding naphthol precursors act alternatives commonly used organic organometallic photocatalysts with applications challenging targets, antimalarial drug artemisinin. This approach was finally transposed in continuous flow reactors where high stability efficiency are demonstrated 23× improvement space-time yield.

Language: Английский

Citations

11
Recent Advances in Organic Photocatalyst‐Promoted Carbohydrate Synthesis and Modification under Light Irradiation DOI Open Access
Jing Wang,

Fan Zhou,

Yu‐Ping Xu

et al.

Chemistry - An Asian Journal, Journal Year: 2025, Volume and Issue: unknown

Published: Jan. 2, 2025

Abstract Photoredox catalysis has been developed as a sustainable and eco‐friendly catalytic strategy, which might provide innovative solutions to solve the current synthetic challenges barriers in carbohydrate chemistry. During last few decades, study of organic photocatalyst‐promoted synthesis modification received significant attention, provides an excellent inexpensive metal‐free alternative photoredox well introduces new fastest‐growing era access complex carbohydrates simply. In this review, we aim overview under light irradiation, is expected directions for further investigation.

Language: Английский

Citations

0
Visible-light promoted photocatalyst-free aerobic α-oxidation of tertiary amines to amides DOI

Xinpeng Xie,

Xuan Guo, Kaikai Qiao

et al.

Organic & Biomolecular Chemistry, Journal Year: 2022, Volume and Issue: 20(41), P. 8031 - 8036

Published: Jan. 1, 2022

A photocatalyst-free, visible-light-induced strategy for the α-oxygenation of tertiary amines by molecular oxygen (1 atm), enabled electron–donor–acceptor (EDA) complexes, has been developed.

Language: Английский

Citations

14